Ssynthesis of Substituted Pyrazolones from Morita-Baylis-Hillman Adducts

S1

Supplementary Material

Morita-Baylis-Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI-MS(/MS)

Rosimeire C. Barcelos, Lucas A. Zeoly, Manoel T. Rodrigues Jr.,

Bruno R. V. Ferreira, Marcos N. Eberlin, Fernando Coelho*

University of Campinas, Institute of Chemistry – PO Box 6154 – 13083-970 – Campinas, SP - Brazil.

SUPPORTING INFORMATION

Table of contents / Page
(1) 1H NMR and 13C NMR spectra for compounds 3a-g, 3j, 5a-h, 4a-h and 6a-h. / S2 – S33
(2) ESI(+)-MS spectra of the reaction monitoring. / S34 – S37

Figure S1.1H NMR spectrum (250 MHz, CDCl3) of compound 3a.

Figure S2.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3a.

Figure S3.1H NMR spectrum (250 MHz, CDCl3) of compound 3b.

Figure S4.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3b.

Figure S5.1H NMR spectrum (250 MHz, CDCl3) of compound 3c.

Figure S6.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3c.

Figure S7.1H NMR spectrum (250 MHz, CDCl3) of compound 3d.

Figure S8.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3d.

Figure S9.1H NMR spectrum (250 MHz, CDCl3) of compound 3e.

Figure S10.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3e.

Figure S11.1H NMR spectrum (250 MHz, CDCl3) of compound 3f.

Figure S12.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3f.

Figure S13.1H NMR spectrum (250 MHz, CDCl3) of compound 3g.

Figure S14.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3g.

Figure S15.1H NMR spectrum (250 MHz, CDCl3) of compound 3j.

Figure S16.13C NMR spectrum (62.5 MHz, CDCl3) of compound 3j.

Figure S17.1H NMR spectrum (250 MHz, CDCl3) of compound 5a.

Figure S18.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5a.

Figure S19.1H NMR spectrum (250 MHz, CDCl3) of compound5b.

Figure S20.13C NMR spectrum (62.5 MHz, CDCl3) of compound5b.

Figure S21.1H NMR spectrum (250 MHz, CDCl3) of compound 5c.

Figure S22.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5c.

Figure S23.1H NMR spectrum (250 MHz, CDCl3) of compound 5d.

Figure S24.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5d.

Figure S25.1H NMR spectrum (250 MHz, CDCl3) of compound 5e.

Figure S26.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5e.

Figure S27.1H NMR spectrum (250 MHz, CDCl3) of compound 5f.

Figure S28.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5f.

Figure S29.1H NMR spectrum (250 MHz, CDCl3) of compound 5g.

Figure S30.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5g.

Figure S31.1H NMR spectrum (250 MHz, CDCl3) of compound 5h.

Figure S32.13C NMR spectrum (62.5 MHz, CDCl3) of compound 5h.

Figure S33.1H NMR spectrum (250 MHz, MeOD) of compound 4a.

Figure S34.13C NMR spectrum (62.5 MHz, MeOD) of compound 4a.

Figure S35.1H NMR spectrum (250 MHz, TFA-d) of compound 4b.

Figure S36.13C NMR spectrum (62.5 MHz, TFA-d) of compound 4b.

Figure S37.1H NMR spectrum (250 MHz, TFA-d) of compound 4c.

Figure S38.13C NMR spectrum (62.5 MHz, TFA-d) of compound 4c.

Figure S39.1H NMR spectrum (250 MHz, TFA-d) of compound 4d.

Figure S40.13C NMR spectrum (62.5 MHz, TFA-d) of compound 4d.

Figure S41.1H NMR spectrum (250 MHz, TFA-d) of compound 4e.

Figure S42.13C NMR spectrum (62.5 MHz, TFA-d) of compound 4e.

Figure S43.1H NMR spectrum (250 MHz, DMSO-d6) of compound 4f.

Figure S44.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound4f.

Figure S45.1H NMR spectrum (250 MHz, DMSO-d6) of compound 4g.

Figure S46.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound 4g.

Figure S47.1H NMR spectrum (250 MHz, DMSO-d6) of compound4h.

Figure S48.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound 4h.

Figure S49.1H NMR spectrum (250 MHz, DMSO-d6) of compound 6a.

Figure S50.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound 6a.

Figure S51.1H NMR spectrum (250 MHz, DMSO-d6) of compound 6b.

Figure S52.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound 6b.

Figure S53.1H NMR spectrum (250 MHz, TFA-d) of compound 6c.

Figure S54.13C NMR spectrum (62.5 MHz, TFA-d) of compound 6c.

Figure S55.1H NMR spectrum (250 MHz, TFA-d) of compound 6d.

Figure 56.13C NMR spectrum (62.5 MHz, TFA-d) of compound 6d.

Figure S57.1H NMR spectrum (250 MHz, TFA-d) of compound 6e.

Figure S58.13C NMR spectrum (62.5 MHz, DMSO-d6) of compound 6e.

Figure S59.1H NMR spectrum (250 MHz, TFA-d) of compound 6f.

Figure S60.13C NMR spectrum (62.5 MHz, TFA-d) of compound 6f.

Figure S61.1H NMR spectrum (250 MHz, TFA-d) of compound 6g.

Figure S62.13C NMR spectrum (62.5 MHz, TFA-d) of compound 6g.

Figure S63.1H NMR spectrum (250 MHz, MeOD) of compound 6h.

Figure S64.13C NMR spectrum (62.5 MHz, MeOD) of compound 6h.

Figura S65. ESI-(+)-MS of compound 3j.

Figura S66. ESI-(+)-MS of reaction at 0 min.

Figura S67. ESI-(+)-MS of reaction at 1h.

Figura S68. Expansion of ESI-(+)-MS of reaction at 1h.

Figura S69. Expansion of ESI-(+)-MS of reaction at 3 h.

Figura S70. ESI-(+)-MS of reaction at 24h.

Figura S71. ESI-(+)-MS(/MS)of the ion m/z 251.

Figura S72. ESI-(+)-MS(/MS)of the ion m/z 269.